CN108390047A - The preparation method and applications of the decrystallized titanium dioxide/graphene composite material in surface - Google Patents

The preparation method and applications of the decrystallized titanium dioxide/graphene composite material in surface Download PDF

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CN108390047A
CN108390047A CN201810262103.3A CN201810262103A CN108390047A CN 108390047 A CN108390047 A CN 108390047A CN 201810262103 A CN201810262103 A CN 201810262103A CN 108390047 A CN108390047 A CN 108390047A
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tio
rgo
composite materials
composite material
preparation
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杨春成
李超
孙昌宁
金波
文子
赵明
李建忱
蒋青
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Jilin University
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Jilin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of preparation method and applications of the decrystallized titanium dioxide/graphene composite material in surface.The composite material is made by two-step method, is as follows：A, using butyl titanate as titanium source, titanium ethylene glycolate ball is generated with glycol reaction, then hydrolyze and generate SA TiO2；B, prepare graphite oxide (GO) aqueous solution using Hummers methods, then with SA TiO2It carries out hydro-thermal reaction and obtains SA TiO2/ RGO composite materials.Negative material of the composite material as lithium ion battery, shows good high rate performance and cyclical stability.In 10A g‑1Current density under, discharge capacity be 135.6mAh g‑1.In 5A g‑1Current density under, cycle 2000 circle after discharge capacity can still remain 98mAh g‑1.The present invention provides new thinking to improve the comprehensive performance of lithium ion battery.

Description

The preparation method and applications of the decrystallized titanium dioxide/graphene composite material in surface
Technical field：
The present invention relates to a kind of decrystallized titanium dioxide/graphene (SA-TiO in surface2/ RGO) composite material preparation side Method and its application in lithium ion battery.
Background technology：
With the fast development in the fields such as aerospace, military equipment, electric vehicle and portable electronic device, people To the comprehensive performance of lithium ion battery (LIBs), more stringent requirements are proposed.In recent years, exploitation has excellent high rate performance and follows The electrode material of ring stability has obtained the extensive concern of researcher.In the negative material of LIBs, TiO2It is rich with resource It is rich, nontoxic, active high and in Li+The advantages such as volume expansion is smaller are inserted into during abjection.But low theoretical capacity, it is low Li+Mobility and ionic conductivity, and the reunion etc. occurred during long-term embedding lithium/de- lithium have seriously affected TiO2's Chemical property.To solve the above-mentioned problems, scientific research personnel puts into a large amount of energy and explores novel TiO2Nanostructure and Its composite material, such as：Mesoporous material, low density structures phase material, TiO2It is carried out with the carbon material of high conductivity compound etc..Most Closely it has been reported that amorphous/disordered material has open diffusion admittance, this not only contributes to the transmission of substance, and advantageous In the diffusion of electronics and ion.Guo et al. has synthesized the decrystallized titanium dioxide/graphene (SA- in surface by photoreduction technology TiO2/ RGO) composite material.This material has surface non crystalline structure, the TiO of nano-scale2Particle and good conductive network, Negative material as lithium ion battery shows excellent chemical property, such as composite material in 3.36A g-1Electric current it is close Under degree, the discharge capacity of 1500 circle of cycle is 108mAhg-1.But photoreduction technology can not be well by TiO2And RGO Closely combine, the chemical property of above-mentioned composite material also needs to be further increased.
Invention content：
The object of the present invention is to provide a kind of decrystallized titanium dioxide/graphene (SA-TiO in surface2/ RGO) composite material Preparation method and its application in lithium ion battery.This material has the following advantages：(1) RGO provides a conduction Network is conducive to the transmission of electronics；(2)SA-TiO2Relative to crystalline state TiO2(C-TiO2) there is better electric conductivity；(3)SA- TiO2With small crystallite dimension, electrode material can be made more fully to be utilized；(4) by forming covalent C-O-Ti Key so that SA-TiO2With RGO can be closer combination.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of decrystallized titanium dioxide/graphene (SA-TiO in surface2/ RGO) composite material preparation method, including it is following Step.
A, SA-TiO is prepared2：2~5ml butyl titanates are added in 10~40ml ethylene glycol, 10~15h, institute are stirred It obtains solution to be added in 100~200ml acetone, continues 1~4h of stirring, then titanium ethylene glycolate is obtained by centrifugation and is distributed it to In aqueous solution containing 20~50ml isopropanols, 30~100 DEG C of 8~12h of stirring, then by the product centrifugal drying 10 after hydrolysis ~12h obtains SA-TiO2；It tests as a comparison, by SA-TiO2600 DEG C of 0.5~3h of annealing obtain crystalline state TiO in air2(C- TiO2)。
B, SA-TiO is prepared2/ RGO composite materials：Prepare graphite oxide (GO) aqueous solution using Hummers methods, then with SA-TiO2It is uniformly mixed, 120~200 DEG C of 3~6h of hydro-thermal process, then by 10~12h of products therefrom centrifugal drying and finally obtains SA-TiO2/ RGO composite materials.
In step a SA-TiO is controlled by adjusting the hydrolysis temperature of titanium ethylene glycolate2Non-crystallization degree.
In step b SA-TiO is controlled by adjusting the hydro-thermal time2With the combination degree of RGO.
According to the composite material that above-mentioned preparation method obtains, the electrode material as lithium ion battery carries out chemical property Test, includes the following steps：
A, the preparation of electrode material：First by active material, i.e. SA-TiO2/ RGO composite materials, with acetylene black and poly- inclined fluorine Ethylene powder is according to mass ratio 8:1:1 is coated on copper foil after mixing in N-Methyl pyrrolidone, then at 80~120 DEG C 10~12h of lower vacuum drying；
B, lithium ion battery assembles：At ambient temperature, using active material as working electrode, lithium piece be used as to electrode/ Reference electrode, diaphragm are 2500 films of Celgard, and electrolyte is the LiPF of 1M6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate In the mixed liquor of ester, dimethyl carbonate and methyl ethyl carbonate, CR2016 types button electricity is assembled into the glove box full of argon gas The water oxygen value in pond, glove box is respectively [O2]<1ppm,[H2O]<1ppm；
C, cyclic voltammetry is carried out using Ivium-n-Stat electrochemical workstations, it is 0.1~0.2mV s to sweep speed-1, electricity Press ranging from 1.0-3.0V；
D, constant current charge-discharge test, voltage range 1.0-3.0V are carried out using LAND CT2001A battery test systems；
E, electrochemical impedance test condition is that frequency range is 100kHz to 10mHz at room temperature.
The solution have the advantages that：
SA-TiO obtained by the present invention2Negative material of/RGO the composite materials as lithium ion battery, shows excellent High rate performance and cyclical stability.
Description of the drawings：
SA-TiO in Fig. 1, the embodiment of the present invention 12, SA-TiO2/ RGO composite materials and C-TiO2It is negative as lithium ion battery The high rate performance curve of pole.
SA-TiO is prepared in Fig. 2, the embodiment of the present invention 12The flow chart of/RGO composite materials.
SA-TiO in Fig. 3, the embodiment of the present invention 12, SA-TiO2/ RGO composite materials and C-TiO2XRD spectrum.
SA-TiO in Fig. 4, the embodiment of the present invention 12The Raman spectrum of/RGO composite materials.
SA-TiO in Fig. 5, the embodiment of the present invention 12/ RGO composite materials, the Raman spectrum of RGO and GO.
SA-TiO in Fig. 6, the embodiment of the present invention 12The hot weight curve of/RGO composite materials.
SA-TiO in Fig. 7, the embodiment of the present invention 12The N of/RGO composite materials2Adsorption/desorption curve and the Size Distribution in hole are bent Line.
SA-TiO in Fig. 8, the embodiment of the present invention 12The full spectrograms of XPS of/RGO composite materials.
SA-TiO in Fig. 9, the embodiment of the present invention 12The XPS spectrum figure of the O 1s of/RGO composite materials.
SA-TiO in Figure 10, the embodiment of the present invention 12The XPS spectrum figure of the Ti 2p of/RGO composite materials.
SA-TiO in Figure 11, the embodiment of the present invention 12The XPS spectrum figure of the C 1s of/RGO composite materials.
SA-TiO in Figure 12, the embodiment of the present invention 12FESEM photos.
C-TiO in Figure 13, the embodiment of the present invention 12FESEM photos.
SA-TiO in Figure 14, the embodiment of the present invention 12The FESEM photos of/RGO composite materials.
SA-TiO in Figure 15, the embodiment of the present invention 12TEM photos.
SA-TiO in Figure 16, the embodiment of the present invention 12The TEM photos of/RGO composite materials.
SA-TiO in Figure 17, the embodiment of the present invention 12HRTEM photos.
SA-TiO in Figure 18, the embodiment of the present invention 12The HRTEM photos of/RGO composite materials.
SA-TiO in Figure 19, the embodiment of the present invention 12The CV curve of/RGO composite materials as negative electrode of lithium ion battery.
In Figure 20, the embodiment of the present invention 1, when current density is 0.5C, SA-TiO2/ RGO composite materials are as lithium ion The constant current charge-discharge curve of battery cathode.
In Figure 21, the embodiment of the present invention 1, SA-TiO2, SA-TiO2/ RGO composite materials and C-TiO2As lithium ion battery The cyclic curve of cathode.
In Figure 22, the embodiment of the present invention 1, SA-TiO2, SA-TiO2/ RGO composite materials and C-TiO2As lithium ion battery The impedance spectrum of cathode.
SA-TiO in Figure 23, the embodiment of the present invention 12The 5Ag in lithium ion battery of/RGO composite electrodes-1Cyclicity It can be with coulombic efficiency curve graph.
SA-TiO in Figure 24, the embodiment of the present invention 22Raman spectrum.
SA-TiO in Figure 25, the embodiment of the present invention 12Raman spectrum.
SA-TiO in Figure 26, the embodiment of the present invention 32Raman spectrum.
Specific implementation mode：
The particular content and specific implementation mode further illustrated the present invention with reference to embodiment, however the embodiment Only implement an example in the present invention, the restriction to technical solution of the present invention cannot be constituted.
Embodiment 1
Preparation process in the present embodiment and steps are as follows：
(1) SA-TiO is prepared2：4ml butyl titanates are added in 20ml ethylene glycol, 12h is stirred, acquired solution is added Into 200ml acetone, continue to stir 2h, then titanium ethylene glycolate is obtained by centrifugation and distribute it to containing 40ml isopropanols and In the mixed solution of 20ml water, then the product centrifugal drying 10h after hydrolysis is obtained SA-TiO by 65 DEG C of stirring 10h2；As Contrast test, by SA-TiO2600 DEG C of annealing 1h obtain crystalline state TiO in air2(C-TiO2)。
(2) SA-TiO is prepared2/ RGO composite materials：It is prepared using Hummers methods and contains 0.008g graphite oxides (GO) water Solution, then with 0.2g SA-TiO2It is uniformly mixed, 150 DEG C of hydro-thermal process 5h, then by products therefrom centrifugal drying 10h and final Obtain SA-TiO2/ RGO composite materials.
(3) the decrystallized titanium dioxide/graphene (SA-TiO in surface that above-mentioned preparation method obtains2/ RGO) composite wood Material carries out electro-chemical test as electrode material, includes the following steps：
A, the preparation of electrode material：First by active material, i.e. SA-TiO2/ RGO composite materials, with acetylene black and poly- inclined fluorine Ethylene powder is according to mass ratio 8:1:1 is coated on copper foil after mixing in N-Methyl pyrrolidone, then at 110 DEG C very The dry 11h of sky；
B, lithium ion battery assembles：At ambient temperature, using active material as working electrode, lithium piece be used as to electrode/ Reference electrode, diaphragm are 2500 films of Celgard, and electrolyte is the LiPF of 1M6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate In the mixed liquor of ester, dimethyl carbonate and methyl ethyl carbonate, CR2016 types button electricity is assembled into the glove box full of argon gas The water oxygen value in pond, glove box is respectively [H2O]<1ppm,[O2]<1ppm；
C, cyclic voltammetry is carried out using Ivium-n-Stat electrochemical workstations, it is 0.2mV s to sweep speed-1, voltage model It encloses for 1.0-3.0V；
D, constant current charge-discharge test, voltage range 1.0-3.0V are carried out using LAND CT2001A battery test systems；
E, electrochemical impedance test condition is that frequency range is 100kHz to 10mHz at room temperature.
SA-TiO2The pattern and structural characterization of/RGO composite materials：
Prepare SA-TiO2The process of/RGO composite materials is as shown in Figure 2.First, by butyl titanate and glycol reaction The titanium ethylene glycolate ball of generation, further hydrolysis obtain SA-TiO2.Then utilize hydro-thermal method by SA-TiO2It combines closely with RGO, This process is along with SA-TiO2Reduction to crystalline transformation and GO.Fig. 3 is SA-TiO2, SA-TiO2/ RGO composite materials and C-TiO2X-ray diffraction (XRD) collection of illustrative plates.It can be seen that SA-TiO2At 25 °, there are one wider characteristic peaks, show TiO2 Nano-particle has extra small size and lower crystallinity.In SA-TiO2After GO hydro-thermal reactions, in composite material SA-TiO2Crystallinity increases, and characteristic peak, which is similar to, has anatase structured (space group:I41/amd(141),JCPDS No.21-1272 C-TiO)2Diffraction maximum.SA-TiO2/ RGO composite materials do not have apparent RGO characteristic peaks, show TiO2It receives Rice corpuscles can prevent the reunion of RGO.Fig. 4 is SA-TiO2The Raman spectrum of/RGO composite materials, wherein belonging to two of RGO Raman characteristic peak is located at 1351 (D bands) and 1585cm-1(G bands).Other feature peak 148cm-1(Eg(1)),399cm-1 (B1g(1)),518cm-1(A1g+B1g(2)) and 639cm-1(Eg(2)) correspond to standard Anatase.Fig. 5 compared GO, RGO and SA- TiO2The Raman spectrum of/RGO.The intensity ratio I of RGOD/IGIt is 0.93, is higher than GO (0.87), this illustrates that RGO has more topologys Defect and disordered structure.For SA-TiO2/ RGO composite materials, ID/IGRatio is further increased to 0.96, this illustrates SA- TiO2In Lacking oxygen replaced by the oxygen in GO, increase the reducing degree of graphene.Furtherly, hydro-thermal method advantageously forms C-O-Ti keys, this not only contributes to SA-TiO2With combining closely for RGO, and is conducive to electronics and transmits between.Fig. 6 For SA-TiO under air2The hot weight curve of/RGO composite materials can be seen that TiO in composite material by analysis2Content Close to 83.2%.Wherein, thermogravimetric curve can be attributed to the volatilization of moisture in preceding 120 DEG C of mass loss, in addition 200~700 The mass loss of DEG C temperature section is attributable to the decomposition of oxygen-containing functional group in RGO.Fig. 7 is N2Suction/desorption curve characterizes SA- TiO2The porosity characteristic of/RGO, BET specific surface area 170.4m2g-1.The size in hole is concentrated mainly on 7.2nm (illustration).This Some holes can not only provide the delivering path of electrolyte, and can alleviate active material in cyclic process due to volume change The stress of generation.
Fig. 8 is SA-TiO2The full spectrograms of XPS of/RGO composite materials, it is known that contain element O, Ti and C in composite material.Fig. 9 It is respectively O 1s, the high-resolution XPS spectrum figure of Ti 2p and C 1s to Figure 11.4 characteristic peak peaks in Fig. 9 correspond respectively to Ti-O Key (529.2eV), Ti-O-C keys (530.7eV), the absorption water (531.4eV) in air and Lacking oxygen (532.5eV).Ti-O-C Bond energy enough makes SA-TiO2It is in close contact between RGO, prevents them from reuniting.Ti in Figure 103+2p1/2,Ti4+2p1/2,Ti3+ 2p3/2And Ti4+2p3/2Bond energy be respectively 457.9,458.9,463.6 and 464.6eV, show in SA-TiO2/ RGO composite materials In exist simultaneously Ti3+And Ti4+。Ti3+And Ti4+The ratio between integral area be 11.7：1, this shows TiO2Surface exist it is a large amount of Lacking oxygen.In fig. 11, there are four peaks for the power spectrum of C 1s.One of peak is attributed to the sp of carbon in 284.5eV2Hydridization.Remaining Peak (286,287.3 and 288.3eV), be attributed to the oxygen-containing functional group remained in GO, such as hydroxyl, carboxyl and epoxides. For SA-TiO2/ RGO composite materials, the characteristic peak of oxygen-containing carbon are not obvious, and show that GO is reduced into RGO.
We are characterized in preparation process by field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) etc. and are mainly produced The structure and pattern of object.Figure 12 and Figure 13 is respectively SA-TiO2And C-TiO2FESEM photos, it can be seen that SA-TiO2Relatively In C-TiO2With better dispersibility.Figure 14 is SA-TiO2The FESEM photos of/RGO composite materials, SA-TiO2It is pinned at RGO Surface.Figure 15 is SA-TiO2The TEM photos of material, it can be seen that SA-TiO2The average thickness of surface amorphous layers is about 2.2nm.Selective electron diffraction (SAED) in illustration is analysis shows TiO2Surface be amorphous.Figure 16 is SA-TiO2/RGO The TEM photos of composite material, as seen from the figure, SA-TiO2It is formed by multiple nanoparticle aggregates.By hydrolyzing ethylene glycol Titanium, the duct between the particle of formation have the function of capillary, are conducive to the infiltration of electrolyte.SA-TiO2TiO in/RGO2Table The average thickness of face amorphous layer is about 1.2nm.As it can be seen that SA-TiO from the high-resolution TEM electromicroscopic photographs of Figure 17 and Figure 182With SA-TiO2The interplanar distance of/RGO is 0.35nm, corresponds to TiO2(101) crystal face.Simultaneously as can be seen that SA-TiO2Crystalline substance Particle size slightly increases after hydro-thermal reaction.This is because in hydrothermal reaction process, amorphous TiO2Pass through atoms permeating weight It is newly distributed to and is grown on existing crystal grain, the thickness for resulting in amorphous layer reduces and crystallite dimension increases.
At ambient temperature, SA-TiO2The Electrochemical Characterization of/RGO composite materials：
Figure 19 is SA-TiO2/ RGO combination electrodes the cyclic voltammetry curve that first five is enclosed in lithium ion battery.In first circle the moon In the scanning process of pole, the anatase TiO of tetragonal phase has been corresponded at the strong peak of 1.71V2To iris Li0.55TiO2Transformation.Exist simultaneously The cathode peak of 1.5V has corresponded to Li0.55TiO2To LiTiO2Transformation.During first circle anodic scan, 1.98V and 2.25V Li has been respectively represented from TiO2Abjection and irreversible electrolyte decomposition in lattice.CV curves third and fourth, this is heavy for five cycle basis It closes, shows the good cyclical stability of composite material.Figure 20 is SA-TiO2/ RGO composite materials are 0.2A g in current density-1Current density under the 1st, 2,50,100 circle constant current charge-discharge curve.The initial discharge capacity of composite material is 433.2mAh g-1.It is respectively 363.2 in the discharge capacity of the 2nd, 50 and 100 circle with the increase of cycle-index, 264 Hes 251.7mAh g-1, it has been more than anatase TiO2Theoretical capacity (168mAh g-1).The higher reason of composite material capacity can return It is following several to receive：(i)SA-TiO2Surface amorphous layers show deformation relaxation, be conducive to keep cathode complete and buffering Li+Volume expansion during insertion/abjection；(ii) RGO itself is conducive to electron-transport, and can contribute a part of appearance Amount；(iii)TiO2Internal resistance can be reduced by Covalent bonding together with RGO.Figure 21 is that current density is 0.2A g-1When, SA- TiO2, SA-TiO2/ RGO composite materials and C-TiO2Cyclic curve as negative electrode of lithium ion battery.It can be seen that passing through After the cycle of 100 circles, SA-TiO2The discharge capacity of/RGO composite materials is 251.7mAh g-1, it is higher than SA-TiO2(109mAh g-1) and C-TiO2(37.1mAh g-1)。SA-TiO2/ RGO composite materials have excellent chemical property may and inside battery Lower resistance is related.Figure 22 is SA-TiO2, SA-TiO2/ RGO composite materials and C-TiO2Resistance as negative electrode of lithium ion battery Anti- collection of illustrative plates.Based on Randles equivalent circuits, SA-TiO2The charge transfer resistance R of/RGO composite materialsctFor 58.5 Ω, it is less than SA-TiO2(93 Ω) and C-TiO2(202 Ω), it was demonstrated that RGO improves the electric conductivity of composite material.Fig. 1 is SA-TiO2, SA- TiO2/ RGO composite materials and C-TiO2As the high rate performance curve of negative electrode of lithium ion battery, as seen from the figure, in different electric currents Under density, SA-TiO2/ RGO composite materials have good high rate performance.In 0.2,0.5,1,2,5 and 10Ag-1Current density Under, SA-TiO2The average discharge capacity of/RGO composite materials be respectively 319.3,267.8,235.1,202,159.2 and 135.2mAh g-1.When current density is 10A g-1When, SA-TiO2Capacity (the 135.6mAh g of/RGO composite materials-1) it is C- TiO2(8.8mAh g-1) 15.4 times.When current density is restored to 0.2A g-1When, SA-TiO2The capacity weight of/RGO composite materials Newly it is restored to 261.9mAh g-1, and remained unchanged in cyclic process afterwards.It is 5A g that Figure 23, which is in current density,-1 When, SA-TiO2Cyclic curve of/RGO the composite materials as negative electrode of lithium ion battery.It can be seen that in 5A g-1Current density Under, SA-TiO2Reversible discharge capacity after 2000 circle of/RGO composite materials cycle is 98mAh g-1, show excellent cyclicity Energy.In conclusion SA-TiO2The structure that/RGO composite materials have faster electrochemical reaction speed and stablize, thus effectively Improve its high rate performance and cyclical stability.The composite material can be as the negative material of lithium ion battery, in Gao Gong Rate field of batteries has certain application prospect.
Embodiment 2
(1) SA-TiO is prepared2：4ml butyl titanates are added in 20ml ethylene glycol, 12h is stirred, acquired solution is added Into 200ml acetone, continue to stir 2h, then titanium ethylene glycolate is obtained by centrifugation and distribute it to containing 40ml isopropanols and In the mixed solution of 20ml water, then the product centrifugal drying 10h after hydrolysis is obtained SA-TiO by 30 DEG C of stirring 10h2；As Contrast test, by SA-TiO2600 DEG C of annealing 1h obtain crystalline state TiO in air2(C-TiO2)。
(2) SA-TiO is prepared2/ RGO composite materials：It is prepared using Hummers methods and contains 0.008g graphite oxides (GO) water Solution, then with 0.2g SA-TiO2It is uniformly mixed, 150 DEG C of hydro-thermal process 5h, then by products therefrom centrifugal drying 10h and final Obtain SA-TiO2/ RGO composite materials.
(3) the decrystallized titanium dioxide/graphene (SA-TiO in surface that above-mentioned preparation method obtains2/ RGO) composite wood Material carries out electro-chemical test as electrode material, includes the following steps：
A, the preparation of electrode material：First by active material, i.e. SA-TiO2/ RGO composite materials, with acetylene black and poly- inclined fluorine Ethylene powder is according to mass ratio 8:1:1 is coated on copper foil after mixing in N-Methyl pyrrolidone, then at 110 DEG C very The dry 11h of sky；
B, lithium ion battery assembles：At ambient temperature, using active material as working electrode, lithium piece be used as to electrode/ Reference electrode, diaphragm are 2500 films of Celgard, and electrolyte is the LiPF of 1M6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate In the mixed liquor of ester, dimethyl carbonate and methyl ethyl carbonate, CR2016 types button electricity is assembled into the glove box full of argon gas The water oxygen value in pond, glove box is respectively [H2O]<1ppm,[O2]<1ppm；
C, cyclic voltammetry is carried out using Ivium-n-Stat electrochemical workstations, it is 0.2mV s to sweep speed-1, voltage model It encloses for 1.0-3.0V；
D, constant current charge-discharge test, voltage range 1.0-3.0V are carried out using LAND CT2001A battery test systems；
E, electrochemical impedance test condition is that frequency range is 100kHz to 10mHz at room temperature.
SA-TiO made from the present embodiment2Raman collection of illustrative plates it is as shown in figure 24.With SA-TiO in embodiment 12Raman collection of illustrative plates (see Figure 25) compares, SA-TiO manufactured in the present embodiment2In 148cm-1(Eg(1)) there are one wider characteristic peaks, show TiO2It receives Rice corpuscles has lower crystallinity.
Embodiment 3
(1) SA-TiO is prepared2：4ml butyl titanates are added in 20ml ethylene glycol, 12h is stirred, acquired solution is added Into 200ml acetone, continue to stir 2h, then titanium ethylene glycolate is obtained by centrifugation and distribute it to containing 40ml isopropanols and In the mixed solution of 20ml water, then the product centrifugal drying 10h after hydrolysis is obtained SA-TiO by 100 DEG C of stirring 10h2；As Contrast test, by SA-TiO2600 DEG C of annealing 1h obtain crystalline state TiO in air2(C-TiO2)。
(2) SA-TiO is prepared2/ RGO composite materials：It is prepared using Hummers methods and contains 0.008g graphite oxides (GO) water Solution, then with 0.2g SA-TiO2It is uniformly mixed, 150 DEG C of hydro-thermal process 5h, then by products therefrom centrifugal drying 10h and final Obtain SA-TiO2/ RGO composite materials.
(3) the decrystallized titanium dioxide/graphene (SA-TiO in surface that above-mentioned preparation method obtains2/ RGO) composite wood Material carries out electro-chemical test as electrode material, includes the following steps：
A, the preparation of electrode material：First by active material, i.e. SA-TiO2/ RGO composite materials, with acetylene black and poly- inclined fluorine Ethylene powder is according to mass ratio 8:1:1 is coated on copper foil after mixing in N-Methyl pyrrolidone, then at 110 DEG C very The dry 11h of sky；
B, lithium ion battery assembles：At ambient temperature, using active material as working electrode, lithium piece be used as to electrode/ Reference electrode, diaphragm are 2500 films of Celgard, and electrolyte is the LiPF of 1M6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate In the mixed liquor of ester, dimethyl carbonate and methyl ethyl carbonate, CR2016 types button electricity is assembled into the glove box full of argon gas The water oxygen value in pond, glove box is respectively [H2O]<1ppm,[O2]<1ppm；
C, cyclic voltammetry is carried out using Ivium-n-Stat electrochemical workstations, it is 0.2mV s to sweep speed-1, voltage model It encloses for 1.0-3.0V；
D, constant current charge-discharge test, voltage range 1.0-3.0V are carried out using LAND CT2001A battery test systems；
E, electrochemical impedance test condition is that frequency range is 100kHz to 10mHz at room temperature.
SA-TiO made from the present embodiment2Raman collection of illustrative plates it is as shown in figure 26.SA- manufactured in the present embodiment as seen from the figure TiO2Characteristic peak 148cm-1(Eg(1)),399cm-1(B1g(1)),518cm-1(A1g+B1g(2)) and 639cm-1(Eg(2)) correspond to standard Anatase shows TiO2Nano-particle has very high crystallinity.

Claims (4)

1. a kind of preparation method of the decrystallized titanium dioxide/graphene composite material in surface, includes the following steps：
A, SA-TiO is prepared2：2~5ml butyl titanates are added in 10~40ml ethylene glycol, 10~15h is stirred, gained is molten Liquid is added in 100~200ml acetone, continues 1~4h of stirring, then by centrifugation obtain titanium ethylene glycolate and distribute it to containing In the aqueous solution of 20~50ml isopropanols, 30~100 DEG C stirring 8~12h, then by the product centrifugal drying 10 after hydrolysis~ 12h obtains SA-TiO2；It tests as a comparison, by SA-TiO2600 DEG C of 0.5~3h of annealing obtain crystalline state TiO in air2(C- TiO2)；
B, SA-TiO is prepared2/ RGO composite materials：Prepare graphite oxide aqueous solution using Hummers methods, then with SA-TiO2It is mixed Uniform, 120~200 DEG C of 3~6h of hydro-thermal process are closed, then by 10~12h of products therefrom centrifugal drying and finally obtain SA-TiO2/ RGO composite materials.
2. a kind of preparation method of the decrystallized titanium dioxide/graphene composite material in surface according to claim 1, special Sign is, SA-TiO is controlled by adjusting the hydrolysis temperature of titanium ethylene glycolate in step a2Non-crystallization degree.
3. a kind of preparation method of the decrystallized titanium dioxide/graphene composite material in surface according to claim 1, special Sign is, SA-TiO is controlled by adjusting the hydro-thermal time in step b2With the combination degree of RGO.
4. according to the composite material that the preparation method described in claim 1 obtains, as lithium ion battery electrode material into Row electrochemical property test, includes the following steps：
A, the preparation of electrode material：First by active material, i.e. SA-TiO2/ RGO composite materials, with acetylene black and Kynoar powder End is according to mass ratio 8:1:1 is coated on copper foil after mixing in N-Methyl pyrrolidone, then the vacuum at 80~120 DEG C Dry 10~12h；
B, lithium ion battery assembles：At ambient temperature, using active material as working electrode, lithium piece is used as to electrode/reference Electrode, diaphragm are 2500 films of Celgard, and electrolyte is the LiPF of 1M6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate, carbon In the mixed liquor of dimethyl phthalate and methyl ethyl carbonate, CR2016 type button cells, hand are assembled into the glove box full of argon gas The water oxygen value of casing is respectively [H2O]<1ppm,[O2]<1ppm；
C, cyclic voltammetry is carried out using Ivium-n-Stat electrochemical workstations, it is 0.1~0.2mV s to sweep speed-1, voltage model It encloses for 1.0-3.0V；
D, constant current charge-discharge test, voltage range 1.0-3.0V are carried out using LAND CT2001A battery test systems；
E, electrochemical impedance test condition is that frequency range is 100kHz to 10mHz at room temperature.
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